C-coated MOF derivative material and preparation method and application thereof

Abstract

The invention relates to the technical field of gas adsorption materials, in particular to a C-coated MOF derivative material and a preparation method and application thereof. The preparation method of the C-coated MOF derivative material comprises the following steps: weighing zirconium oxychloride octahydrate and organic acid, adding N, N-dimethylformamide and glacial acetic acid, and stirring for 3.0-6.0 hours at the temperature of 50-120 DEG C while keeping the temperature, so as to form a reddish brown homogeneous precursor solution; the preparation method comprises the following steps: adding tetrakis (4-carboxyphenyl) porphyrin and ethidene diamine into a reaction kettle, adding tetrakis (4-carboxyphenyl) porphyrin and ethidene diamine under a stirring condition, continuously stirring and reacting for 20-40 minutes, transferring the obtained mixed solution into the reaction kettle, heating to 150-250 DEG C, reacting for 1.0-5.0 days at a constant temperature, naturally cooling to 20-40 DEG C, centrifugally separating the obtained reaction solution to obtain a lower-layer reaction product, and washing and drying the reaction product to obtain the C-coated MOF derivative material. The C-coated MOF derivative material disclosed by the invention shows efficient adsorption performance, relatively high adsorption efficiency and relatively high desorption efficiency on toluene.

Description

Technical Field

[0001] This invention relates to the field of gas adsorption materials technology, and in particular to a C@MOF derived material, its preparation method and application. Background Technology

[0002] In advanced processes for ultra-large-scale integrated circuits (ULSI), the control of trace gaseous contaminants in the wafer fabrication environment has become a core factor determining device reliability. Toluene, a key component of photoresist solvents, causes a chain reaction of failures in multiple critical process stages due to its high volatility and non-polar molecular properties: in extreme ultraviolet lithography (EUV), toluene vapor condenses within the projection optics system to form carbonaceous deposits, leading to decreased specular reflectivity and consequently linewidth variations; in chemical vapor deposition (CVD), toluene molecules compete with silane precursors for adsorption, forming a certain thickness of organic residue layer on the wafer surface, reducing the gate oxide breakdown voltage. As process nodes advance to below 3nm, the requirements for toluene concentration control in cleanrooms at wafer fabs have increased to sub-ppb levels, posing unprecedented challenges to traditional purification technologies.

[0003] Current purification systems for gaseous molecular pollutants (AMCs), including VOCs such as toluene, primarily rely on a three-stage filtration architecture, with the terminal adsorbent material handling molecular-level retention. Activated carbon, as a traditional adsorbent, possesses a specific surface area of ​​1000-3000 m² / g (as described in patent CN118384855A), but its micropore distribution is discrete and its surface functional groups are randomly distributed, resulting in insufficient selectivity for non-polar toluene molecules. Under conditions where relative humidity (RH) exceeds 50%, competitive adsorption of water molecules leads to a severe decrease in the dynamic adsorption capacity of toluene. Ion exchange resins (e.g., patent CN105174243A) achieve chemical adsorption through the charge interaction between sulfonic acid groups and polar molecules; however, limited by the rigid structure of the resin skeleton (such as the styrene-divinylbenzene crosslinked system), their effective specific surface area is typically below 300 m² / g, and their affinity for toluene approaches zero. In sub-ppb toluene purification, the dynamic adsorption breakthrough time is less than minutes. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a C@MOF derived material, its preparation method and application, so as to at least solve the problem of low dynamic adsorption capacity of toluene in existing toluene adsorbent materials.

[0005] The following is a summary of this disclosure to provide a basic understanding of some aspects. This summary is not intended to identify key or important elements, nor is it intended to limit the implementation or any aspects of the claims. Furthermore, this summary provides a simplified overview of some aspects that can be described in more detail in other parts of this disclosure.

[0006] The present invention solves the above-mentioned technical problems through the following technical means:

[0007] The first aspect of this invention provides a method for preparing C@MOF-derived materials, comprising the following steps:

[0008] Weigh zirconium oxychloride octahydrate and organic acid, add N,N-dimethylformamide and glacial acetic acid, and stir at 50-120℃ for 3.0-6.0 h to form a reddish-brown homogeneous precursor solution. Under stirring conditions, add tetrakis(4-carboxyphenyl)porphyrin and ethylenediamine, and continue stirring for 20-40 min. Transfer the resulting mixed solution to a reaction vessel, heat to 150-250℃, and react at a constant temperature for 1.0-5.0 days. After natural cooling to 20-40℃, centrifuge the resulting reaction solution to obtain the lower reaction product. Wash and dry the reaction product to obtain C@MOF derived material.

[0009] Zirconium oxychloride octahydrate dissociates into Zr under heating conditions in a DMF / glacial acetic acid mixed solvent. 4 ⁺ and Cl⁻ are counterions; tannic acid (TA), gallic acid (GA), and citric acid (CA) all contain multiple carboxyl / phenolic hydroxyl groups, and react with Zr. 4 ⁺ Multidentate coordination occurs, forming a stable reddish-brown homogeneous complex, avoiding Zr 4 ⁺ Direct hydrolysis produces ZrO2 precipitate; glacial acetic acid provides a weakly acidic environment, inhibiting Zr... 4 ⁺ Hydrolysis (Zr 4 ⁺ It readily hydrolyzes to Zr(OH)4 under neutral / alkaline conditions, and also acts as a coordination aid, reacting with Zr 4 ⁺ Weak coordination modifies the complex structure. Tetra(4-carboxyphenyl)porphyrin (TCCP) contains four carboxyl groups and is a tetradentate organic ligand, which interacts with Zr. 4 The Zr-O coordinate bonds of the metal nodes form a three-dimensional porous MOF structure (Zr-TCPP porphyrin MOF), and the π-π conjugation of the porphyrin ring gives the solution a deep green color. Ethylenediamine, on the one hand, acts as an acid in the base neutralization system (H⁺ from the dissociation of glacial acetic acid and organic acids), promoting the deprotonation of the carboxyl group of TCPP to TCPP. 4 ⁻, Enhancement with Zr 4 Zr's coordination ability, on the one hand, acts as a nitrogen / carbon source, undergoing condensation / carbonization reactions with organic acids and TCPP at high temperatures to generate carbonized polymer dots (CPDs) in situ; on the other hand, it acts as a structure-directing agent, adjusting the pore structure and crystallinity of MOFs. Furthermore, at high temperatures, the solvent (DMF / glacial acetic acid) is in a subcritical state, lowering the activation energy and promoting the reaction of Zr. 4⁺ Coordination polymerization with TCPP accelerates the generation and encapsulation of CPDs; the in-situ generated CPDs are small in size (nanometer-scale) and can enter the channels / gaps of Zr-TCPP MOF to form C@MOF-derived materials.

[0010] In conjunction with the first aspect, in some embodiments, the molar ratio of the zirconium oxychloride octahydrate to the organic acid is 1:(0.08 to 0.24).

[0011] In conjunction with the first aspect, in some embodiments, the organic acid is selected from at least one of tannic acid, gallic acid, and citric acid.

[0012] In conjunction with the first aspect, in some embodiments, the molar volume ratio of zirconium oxychloride octahydrate and N,N-dimethylformamide is 1 mmol: 30 mL, and the volume ratio of N,N-dimethylformamide and glacial acetic acid is 1: (0.1 to 0.125).

[0013] In conjunction with the first aspect, in some embodiments, the molar ratio of zirconium oxychloride octahydrate to tetra(4-carboxyphenyl)porphyrin is 1:(1-3), and the molar ratio of tetra(4-carboxyphenyl)porphyrin to ethylenediamine is (2-1):1.

[0014] In conjunction with the first aspect, in some embodiments, the mixture is transferred to a reaction vessel and heated to 150–250°C at a rate of 3–8°C / min.

[0015] In conjunction with the first aspect, in some embodiments, the reaction solution is centrifuged at 6000-10000 rpm for 5-15 min to remove the supernatant and separate the lower layer reaction product.

[0016] In conjunction with the first aspect, in some embodiments, the reaction product is repeatedly washed with N,N-dimethylformamide 2 to 5 times, then washed with deionized water 2 to 5 times, and finally dried at 60 to 120°C for 12 to 24 hours to obtain C@MOF derived material.

[0017] A second aspect of the present invention provides a C@MOF-derived material, which is prepared using the preparation method described in the first aspect.

[0018] The third aspect of this invention provides the application of a C@MOF-derived material as described in the second aspect in toluene adsorbent materials.

[0019] One or more technical solutions provided in the embodiments of the present invention have at least the following technical effects or advantages:

[0020] (1) The C@MOF derivative material of the present invention exhibits high efficiency adsorption performance for toluene. The "carbonized polymer dots" encapsulated in the MOF channels form a water molecule repulsion layer through the ultra-high hydrophobic surface (contact angle >105°), blocking the competitive adsorption of water molecules, thereby improving the adsorption capacity for toluene. The test showed that the adsorption capacity for toluene was as high as 526 mg / g, which is about 113% higher than that of Zr-MOF without encapsulation of "carbonized polymer dots".

[0021] (2) The C@MOF derivative material of the present invention exhibits high adsorption efficiency for toluene. On the one hand, the sp² carbon domain of C strongly adsorbs toluene through π-π interaction; on the other hand, the porous structure of Zr-MOF achieves precise confinement and selective and efficient adsorption of toluene.

[0022] (3) The C@MOF derivative material of the present invention exhibits high desorption efficiency for toluene. The carbonized polymer dots and porphyrin ligands therein can absorb light energy and convert it into heat and electrons, attacking the adsorbed toluene and causing it to desorb rapidly, thereby reducing industrial energy consumption and significantly improving cycle life.

[0023] (4) The preparation method of the present invention uses simple and readily available materials and the process is simple and easy to operate. Attached Figure Description

[0024] Figure 1 This is a nitrogen adsorption-desorption curve of C@Zr-MOF-1;

[0025] Figure 2 This is a nitrogen adsorption-desorption curve of C@Zr-MOF-2;

[0026] Figure 3 This is a nitrogen adsorption-desorption curve of C@Zr-MOF-3;

[0027] Figure 4 These are nitrogen adsorption-desorption curves for Zr-MOF;

[0028] Figure 5 The graph shows the dynamic adsorption curves of C@Zr-MOF-1, C@Zr-MOF-2, C@Zr-MOF-3 and Zr-MOF on toluene.

[0029] Figure 6 This is a graph showing the adsorption capacity of C@Zr-MOF-1, C@Zr-MOF-2, C@Zr-MOF-3, and Zr-MOF for toluene. Detailed Implementation

[0030] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0031] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0032] The C@MOF-derived material of this invention is a carbonized polymer dot@porphyrin MOF composite material system. Through a three-pronged synergistic mechanism of "hydrophobic barrier-π bond enhancement-photothermal regeneration," it overcomes the technical bottleneck of efficient toluene removal and low-energy regeneration under high humidity conditions, providing a reliable AMC control solution for advanced processes below 3nm. Specifically, a "bottling in a ship" strategy is adopted, where a template agent is added during MOF material preparation to achieve "site-specific carbonization" in a one-pot reaction, and the resulting "carbonized polymer dots" are encapsulated within the MOF channels to obtain the C@MOF-derived material.

[0033] Specifically, please refer to the following example:

[0034] Example 1

[0035] The preparation method of the C@MOF-derived material in this embodiment is as follows:

[0036] Weigh 0.64 g of zirconium oxychloride octahydrate (ZrOCl2·8H2O, 2.0 mmol) and 0.28 g of citric acid (TA, 0.16 mmol) into a beaker, add 60 mL of N,N-dimethylformamide and 6 mL of glacial acetic acid, and stir magnetically at 400 rpm for 4.0 h in an oil bath at 80 °C to form a reddish-brown homogeneous precursor solution. Under magnetic stirring, 1.48 g of tetrakis(4-carboxyphenyl)porphyrin (TCPP, 2.0 mmol) and 60 μL of ethylenediamine (1.0 mmol) were added, and stirring was continued for 30 min until the solution turned dark green. The resulting mixed solution was transferred to a polytetrafluoroethylene-lined reactor and heated to 200 °C at a rate of 5 °C / min. The reaction was carried out at this temperature for 5.0 days. After the reaction was completed, the mixture was naturally cooled to 25 °C, and the reaction product was separated by centrifugation at 8000 rpm for 10 min. The reaction product was washed three times with DMF and then three times with deionized water. Finally, it was dried at 80 °C for 24 h to obtain the C@MOF-derived material, denoted as C@Zr-MOF-1.

[0037] Example 2

[0038] In this embodiment, the amount of citric acid used in Example 1 was replaced with 0.56g, while other steps and conditions remained unchanged. The final product was denoted as C@Zr-MOF-2.

[0039] Example 3

[0040] In this embodiment, the amount of citric acid used in Example 1 was replaced with 0.84g, while other steps and conditions remained unchanged. The final product was denoted as C@Zr-MOF-3.

[0041] Example 4

[0042] The preparation method of the C@MOF-derived material in this embodiment is as follows:

[0043] Weigh 0.64 g of zirconium oxychloride octahydrate and 0.54 g of tannic acid into a beaker, add 60 mL of N,N-dimethylformamide and 6.6 mL of glacial acetic acid, and stir magnetically at 500 rpm for 6.0 h in an oil bath at 50 °C to form a reddish-brown homogeneous precursor solution. Under magnetic stirring, 2.96 g of tetrakis(4-carboxyphenyl)porphyrin and 180 μL of ethylenediamine were added, and stirring was continued for 20 min. The solution turned dark green. The resulting mixed solution was transferred to a polytetrafluoroethylene-lined reactor and heated to 150 °C at a rate of 3 °C / min. The reaction was carried out at this temperature for 5.0 days. After the reaction was completed, the solution was naturally cooled to 20 °C and centrifuged at 6000 rpm for 15 min. The supernatant was removed, and the reaction product was separated. The reaction product was washed twice with DMF and then twice with deionized water. Finally, it was dried at 60 °C for 24 h to obtain the C@MOF-derived material, denoted as C@Zr-MOF-4.

[0044] Example 5

[0045] The preparation method of the C@MOF-derived material in this embodiment is as follows:

[0046] 0.64 g of zirconium oxychloride octahydrate and 0.07 g of gallic acid were weighed into a beaker, and 60 mL of N,N-dimethylformamide and 7.5 mL of glacial acetic acid were added. The mixture was magnetically stirred at 400 rpm for 3.0 h in an oil bath at 120 °C to form a reddish-brown homogeneous precursor solution. Under magnetic stirring, 4.5 g of tetrakis(4-carboxyphenyl)porphyrin and 270 μL of ethylenediamine were added, and stirring was continued for 40 min. The solution turned dark green. The resulting mixed solution was transferred to a polytetrafluoroethylene-lined reactor and heated to 250 °C at a rate of 8 °C / min. The reaction was maintained at this temperature for 1.0 day. After the reaction was completed, the mixture was naturally cooled to 40 °C, and the reaction product was separated by centrifugation at 10,000 rpm for 5 min. The reaction product was washed repeatedly with DMF 5 times, then washed with deionized water 5 times, and finally dried at 120 °C for 12 h to obtain the C@MOF-derived material, denoted as C@Zr-MOF-5.

[0047] Comparative Example 1

[0048] In this comparative example, the amount of citric acid used in Example 1 was replaced with 0g, that is, no citric acid was used. All other steps and conditions remained unchanged, and the final product was denoted as Zr-MOF.

[0049] The C@Zr-MOF-1 of Example 1, the C@Zr-MOF-2 of Example 2, and the C@Zr-MOF-3 of Example 3, as well as the Zr-MOF of Comparative Example 1, were used as samples for structural characterization and performance testing as follows:

[0050] (1) Specific surface area and pore size test analysis

[0051] Using a Belserp MAX II analyzer, the BET surface area and pore structure of the material were tested at -195°C using N2 adsorption and desorption. Gas adsorption was performed, and the total surface area was determined using the Brunol-Emmett-Taylor (BET) equation. The nitrogen adsorption-desorption curves of C@Zr-MOF-1 obtained from the tests are shown below. Figure 1 As shown, the nitrogen adsorption-desorption curves of C@Zr-MOF-2 are as follows: Figure 2 As shown, the nitrogen adsorption-desorption curves of C@Zr-MOF-3 are as follows: Figure 3 As shown, the nitrogen adsorption-desorption curves of Zr-MOF are as follows: Figure 4 As shown in Table 1, the final calculated specific surface area, pore volume, and pore diameter are shown in Table 1.

[0052] Table 1. Test results of specific surface area, pore volume, and pore size of the samples.

[0053] sample <![CDATA[BET(m 2 / g)]]> <![CDATA[Pore volume (cm 3 / g)]]> Aperture (nm) C@Zr-MOF-1 2636 2.42 1.84 C@Zr-MOF-2 2671 2.22 1.66 C@Zr-MOF-3 2733 1.79 1.32 Zr-MOF 2599 2.14 1.65

[0054] Combined with Table 1 and Figure 1-4It can be seen that C@Zr-MOF-1 of Example 1, C@Zr-MOF-2 of Example 2, C@Zr-MOF-3 of Example 3, and Zr-MOF of Comparative Example 1 all have high specific surface areas.

[0055] (2) Dynamic adsorption performance test of toluene

[0056] Toluene adsorption was tested on the material using a UTEST static adsorption apparatus. Initial efficiency: test airflow (12 L / min), test resistance (100 Pa), test concentration (600 ppb); Poisoning capacity: test airflow (15 L / min), test resistance (100 Pa), test concentration (10 ppm). The adsorption capacity was calculated by integrating the breakthrough curve, using the following formula:

[0057]

[0058] In the formula, q (g / g) is the maximum adsorption capacity, F (mL / min) is the total gas flow rate, and C0 and C (mg / m³) are also present. 3 The inlet and outlet concentrations of toluene are denoted as m(g) and t(t), respectively. s (min) represents the adsorption time. The dynamic adsorption curve of the sample for toluene is shown below. Figure 5 As shown, the adsorption capacity of the sample for toluene is as follows: Figure 6 As shown.

[0059] Combination Figure 5 and Figure 6 It can be seen that the C@Zr-MOF derivative material prepared in the embodiments of the present invention exhibits high adsorption performance for toluene: the adsorption breakthrough time of the three groups of samples in Examples 1, 2 and 3 is successively delayed, and the adsorption capacity for toluene reaches 356 mg / g, 424 mg / g and 526 mg / g respectively, while the comparative sample is only 247 mg / g.

[0060] (3) Photothermal desorption performance test

[0061] The photothermal desorption performance of toluene was tested using a self-built fixed-bed adsorption-desorption reactor. The specific procedure is as follows: First, a pretreated and activated sample (100 mg) was placed in a quartz reactor, and toluene vapor (400 ppm) was introduced and adsorbed until saturation at 25°C. Then, the desorption stage was initiated: under a constant temperature of 80°C, a xenon lamp was turned on to irradiate the material surface, and the dynamic change of the outlet toluene concentration was monitored to calculate the toluene desorption rate. The results are shown in Table 2.

[0062] Table 2. Results of Photothermal Desorption Performance Test

[0063] sample Desorption rate (%) 90% desorption time (min) Desorption rate (%) after 5 cycles C@Zr-MOF-1 97.4 21 97.2 C@Zr-MOF-2 98.2 16 98.0 C@Zr-MOF-3 99.8 12 99.5 Zr-MOF 93.6 35 92.4

[0064] The data in Table 2 show that the C@Zr-MOF derivative material prepared by this invention can absorb light energy and convert it into heat and electrons, attacking the adsorbed toluene and causing it to desorb rapidly. The desorption time is significantly shortened by 90%, thereby reducing industrial energy consumption. At the same time, the desorption rate of the C@Zr-MOF derivative material prepared by this invention is still as high as 99.5% after 5 cycles, which shows strong regeneration performance.

[0065] In summary, the C@Zr-MOF derivative material prepared in this invention exhibits high efficiency in adsorbing toluene. Therefore, the C@Zr-MOF derivative material prepared in this invention can be used in toluene adsorption materials.

[0066] The foregoing description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe every conceivable combination of components or methods; however, those skilled in the art will understand that many other combinations and arrangements are possible. Therefore, this specification is intended to cover all such changes, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, with regard to the use of the term "comprising" in the detailed description or claims, the term is intended to be inclusive in a manner similar to the term "including," as interpreted when "comprising" is used as a transitional word in the claims.

[0067] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A method for preparing C@MOF-derived materials, characterized in that, Includes the following steps: Weigh zirconium oxychloride octahydrate and organic acid, add N,N-dimethylformamide and glacial acetic acid, and stir at 50-120℃ for 3.0-6.0 h to form a reddish-brown homogeneous precursor solution. Under stirring conditions, add tetrakis(4-carboxyphenyl)porphyrin and ethylenediamine, and continue stirring for 20-40 min. Transfer the resulting mixed solution to a reaction vessel, heat to 150-250℃, and react at a constant temperature for 1.0-5.0 days. After natural cooling to 20-40℃, centrifuge the resulting reaction solution to obtain the lower reaction product. Wash and dry the reaction product to obtain C@MOF derived material.

2. The method for preparing a C@MOF-derived material according to claim 1, wherein, The molar ratio of zirconium oxychloride octahydrate to organic acid is 1:(0.08-0.24).

3. The method for preparing a C@MOF-derived material according to claim 2, wherein, The organic acid is selected from at least one of tannic acid, gallic acid, and citric acid.

4. The method for preparing a C@MOF-derived material according to claim 1, wherein, The molar volume ratio of zirconium oxychloride octahydrate and N,N-dimethylformamide is 1 mmol: 30 mL, and the volume ratio of N,N-dimethylformamide and glacial acetic acid is 1: (0.1 to 0.125).

5. The method for preparing a C@MOF-derived material according to claim 1, wherein, The molar ratio of zirconium oxychloride octahydrate to tetra(4-carboxyphenyl)porphyrin is 1:(1-3), and the molar ratio of tetra(4-carboxyphenyl)porphyrin to ethylenediamine is (2-1):

1.

6. The method for preparing a C@MOF-derived material according to claim 1, wherein, The mixture is transferred to a reaction vessel and heated to 150–250°C at a rate of 3–8°C / min.

7. The method for preparing a C@MOF-derived material according to claim 1, wherein, The reaction solution was centrifuged at 6000-10000 rpm for 5-15 min, the supernatant was removed, and the lower layer of reaction product was obtained.

8. The method for preparing a C@MOF-derived material according to claim 7, wherein, The reaction product was washed repeatedly with N,N-dimethylformamide 2 to 5 times, then washed with deionized water 2 to 5 times, and finally dried at 60 to 120°C for 12 to 24 hours to obtain C@MOF derivative material.

9. A C@MOF-derived material, characterized in that, It is prepared by the preparation method described in any one of claims 1-8.

10. The application of the C@MOF derived material according to claim 9 in toluene adsorbent materials.

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